DE69730445T2 - Night luminescent or fluorescent natural stone - Google Patents

Description

Technical area

The Invention of this application relates to a noctilucent or fluorescent artificial stone. In particular, the invention relates this application, an artificial stone with night lighting properties, such as Light storage properties or light emission properties, accompanied by ultraviolet radiation absorption, which is a building material, Stage material as a direction indicator or position light for night decoration properties, Dark field environment, etc.

State of the art

So far is known artificial stone by crushing natural stone, mixing of the pounded Natural stone with resin, etc., to produce grinding and hardening. And what As far as this artificial stone is concerned, various attempts have been made give it the appearance of marble, granite, etc., and further it also an improved hardness and to give strength.

When a trial, the function and performance of such an artificial stone It was suggested to give it an optical function giving a noctilucent substance of light storage material, Fluorite substance, which shines through the stored light, etc. or fluorescent substance of ultraviolet radiation emitting light Material, etc., as a by-product of ultraviolet radiation absorption Emitted light, is used. This attempt, a solidifying Resin component as a binder for to mix the artificial stone with fluorescent substance or solidifying unsaturated polyester, Methacrylic resin, glass etc. with light-storing fluorescent Substance or ultraviolet radiation fluorescent substance Strontium aluminate, etc., is mixed to form artificial stone Using one of these crushed substances performed as an aggregate.

in the Trap of conventional noctilucent fluorite-emitting or fluorescent artificial stone with Light storage material, etc., only on that part of the binder resin component or of the aggregate located on the surface part of the artificial stone, by any of the above Method works, however, it is a disadvantage that light storage material etc., which is contained inside the artificial stone molded body, at all not working. Fluorescent material from light storage material etc. is very expensive, and since even the addition of a small amount the total cost of the artificial stone product about 3 to 10 times elevated, is more conventional Artificial stone containing fluorescent substance inside, the not functioning as such, in practice cost-inefficient, and because of the disadvantage that because the light emission on the area of the surface layer of the artificial stone limited remains, no sufficient light emission thickness can be obtained it comes to the problem that his Use due to the high cost and the limited light emission performance extremely restricted is.

If to reduce costs, the amount of addition is reduced arises on the other hand the problem that the Functional effect of light emission or light storage only rarely received.

Around to improve the lighting function of artificial stone, it was therefore hoped To be able to develop a new artificial stone whose functional effect is better and is able to have a sufficient light emission thickness to achieve, not only on the surface, by reducing costs less noctilucent or fluorescent substance from light storage material etc. is used.

Disclosure of the invention

Accordingly, presents the invention of this application to solve the above problem an artificial stone available, containing the inorganic aggregate and resin, the noctilucent or fluorescent artificial stone at least partially inorganic Comprises aggregate, which transparent inorganic aggregate in a proportion of 5-65% by weight the total amount of the composition by firing or coating at normal temperature of a surface with noctilucent substance from light storage material, fluorite substance with the storage light or fluorescent substance having light-emitting properties, accompanied by ultraviolet radiation absorption.

Short description of drawings

1 The accompanying drawing is a sectional view showing the construction of the artificial stone of this invention.

Best embodiment to carry out the invention

The Invention of this application will be described in more detail below by us described.

The Composition of the artificial stone of this invention contains as a basic component inorganic aggregate and resin. There is also at least one Part of the contained inorganic aggregate from a transparent inorganic aggregate with a surface layer of noctilucent or fluorescent substance, wherein a feature of this artificial stone Is that it is in a proportion of 5-65 Wt .-% of the total amount of artificial stone composition is present.

If this proportion is less than 5 wt .-%, are not sufficient Achieves light emission properties, in particular no good light emission density. And when the 65 wt .-% exceeded this is in relation to the light emission characteristics not economical.

What As far as the inorganic aggregate is concerned, it does not necessarily have to be completely transparent but generally should be more than 5% by weight, preferably 10-90 Wt .-%, in particular 20-80 Wt .-%, be transparent inorganic aggregate, with noctilucent, fluoride luminescent or fluorescent substance is coated.

Further be by size division (Particle diameter) of the inorganic aggregate, the following two species are illustrated as preferred. The one is a component of small inorganic particles of 5-70 mesh size as the main component, this component being selected from small inorganic particles from the minerals quartz stone, olivine, feldspar, pyroxene and mica etc., from natural stone granite, from metamorphic rock, etc., porcelain, Glass, metal, etc.

And together with this small-particle component is preferably a finely divided component of less than 100 mesh used. As an an example for this finely divided component will be different types of natural or artificial called finely divided components. For example, calcium carbonate, aluminum hydroxide, Fumed silica etc. an easily available finely divided component.

As well It is allowed, as part of this finely divided component, a manganese dioxide, Titanium dioxide, zirconium silicate, iron oxide component, etc. to add to adjust the hue, or an antimony trioxide, boron compound, Bromine compound component, etc. to flame retardance / non-flammability properties to rent.

The The aforementioned small-scale component is mainly used the appearance and the physical properties of the artificial stone to get. In particular, when a part is exposed, in combination with other components, carries they mainly to the color and structure.

Further it is necessary in this small-scale component of this invention one in which at least a part is transparent than the one to use their surface by firing or coating at normal temperature with noctilucent Substance with light storage properties, fluorite substance, the lit by the stored light, etc. or more fluorescent Substance having light emission properties accompanied by ultraviolet radiation absorption, is provided. In other words, should be a part or the entire amount of the small-scale component be transparent inorganic aggregate whose surface with noctilucent substance or fluorescent substance coated is. As a suitable small-scale component for the inorganic aggregate with such transparency, for example, glass, quartz stone, etc. called.

at the small component to be incorporated in the composition it is desirable a proportion (by weight) of 10-100% transparent inorganic Aggregate with a surface coating from the above noctilucent substance or fluorescent To use substance.

The finely divided component is substantially smaller than 100 mesh as compared with the small particle component, and it occupies a position where it penetrates between the individual particles of the small-sized components and fills the space between the particles, which contributes to the artificial stone properties such as To give hardness and flexibility. It is preferable that the weight ratio of the small particle component to give to this finely divided component 0.5: -5: 1, preferably 1: 1-4: 1.

The Resin component can also be made from a wide variety of thermosetting Resins are selected.

When Example can Acrylic resin, methacrylic resin, unsaturated Polyester resin, etc. may be mentioned. Of these, for example, is methacrylic resin from the standpoint of hardness, Strength etc. seen from suitable. It is desirable that the formulation ratio of Resin component is less than 15 wt .-%, and preferably not more than 10 wt .-% of the total composition. This resin component serves to the small-particle component, which with the finely divided Component the above framework forms, to enclose, in order to give the product as a whole elasticity or tensile strength, when the artificial stone is completed.

Therefore is the proportion of inorganic aggregate to be used the small-scale component and the finely divided component, limited. This means, the proportion by weight should not be less than 85%, preferably not less than 90%. If it exceeds 95%, the product becomes brittle, and it is only possible, to get a hard-to-use product. If he is lower than 85%, the product is so soft that the stone-like properties can not be obtained unfortunately the scope of application is the same as for resin plates.

This implies that the other component, neither small-particle component nor finely divided Natural stone component, etc. is, d. H. the resin component, in a weight of at most 15% should be present in the product.

If the resin component exceeds about 15%, The product is plastic-like, and the appearance of the artificial stone is only by name. The excessive reduction the resin component has the consequence that the appearance of the Although a more natural product Shade gets, however, the product is brittle and for the use becomes unsuitable. Therefore, the resin component should preferably 3-10 Wt .-% amount.

In the embodiment of this invention, the constitutional relationship of these components is important. Of particular importance is the constitutional ratio of the resin component and the other components. A feature of this invention is that a product of high density and compact structure can be obtained, where high density herein means that the particulate component and finely divided component are present in the cast stone product at high density, the value being, for example, the range of conventional Artificial stone exceeds, for example, a density higher than 2.2 g / cm ³ .

And It is another feature of the embodiment that in this Invention at least a portion of the small-scale component, which the framework component by firing or coating at normal temperature with a noctilucent substance or a fluorescent substance Substance is provided, as described above.

at A transparent inorganic aggregate is especially a fired one Coating the small-particle component prepared so that the particle surface of the transparent small-particle component with several γm to several ten μm, for example 5-50 μm, especially preferably about 20-40 μm, coated is. More specifically, it is possible to perform the coating by firing at high temperature of 120-1200 ° C.

The noctilucent substance, the fluorite substance or the fluorescent Substance to be fired can be selected from the group consisting of noctilucent substances or fluorite substances, which shine with the stored light, and fluorescent substances, the light by ultraviolet radiation or light absorption properties emit, such. As strontium aluminate, zinc sulfate, etc.

The Burning is not usual known method; it is possible, the transparent inorganic aggregate, for example, the above small particle component, with dispersion solution or paste, in which for example, powdered granules of strontium aluminate light storage material etc., to mix, to dry and to burn.

When coating by normal temperature coating, the coating is carried out by Mitver Use of transparent tacky substance (binder) for the above-mentioned dispersion solution or paste.

at As mentioned above, according to the present invention, it is desirable to use the inorganic small particle Component of a certain size. This means, the inorganic particulate particulate component should be the one above called size of 5-70 mesh have. If you add color or want to remove by adding a colored and a colorless component used, it is conceivable the size of small particles by presence or to change the absence of color, being excessive use an extreme difference in size should be avoided as this reduces the strength of the product.

on the other hand should be the size of the particles the finely divided component as mentioned above be less than 100 mesh. It should be such that the Particles sufficiently between the particles of the small-particle component can penetrate. More specifically, 150-250 Mesh preferred.

These However, the invention is not limited to a composition whose Contains inorganic aggregate which, as mentioned above, in divided a small-scale component and a finely divided component is.

What important in the high density artificial stone of this invention, is that, except in special Cases, it he wishes is that this inorganic aggregate components uniform in each part of the Products are dispersed.

And it is desirable that the Outside surface of the Product is polished or roughened. In practice, it is preferable to make them so that one broken fragmentary component is exposed.

The Polishing is a convenient method in practice to dense Structural state of high-density artificial stone with depth effect, the to expose this invention. Of course it is possible to have a part the surface to polish the product, exposing the small particle component is going to make the difference to other parts of the same surface as Pattern to use.

at The production of artificial stone is a significant problem, one any desired color or any desired one Create construction properties. Granite or marble is a goal because it is difficult to make natural stone products and there her color shine beautiful is. In this invention, it is more transparent by use Particles as a small-scale component possible to use an artificial stone to preserve the luster and appearance of granite or marble as it is possible is, small particle by crushing of quartz-based natural stone were obtained as a small-particle component.

little one Particles by crushing of quartz-based natural stone are in many cases colorless and transparent. Even if they are not transparent, there is many that give some transparency.

By Addition of inorganic dye or organic pigment, such as z. As azo pigment, phthalocyanine pigment, etc., or various Dyes it is possible a unique color with uniform color, depth and uniformity To create shine.

at The artificial stone composition of this invention, it is also possible, the Product to give color by colored particles as a color component with the particles of the small-particle component with approximately the same Size mixed become.

On in any case it is possible much easier to ensure the reproducibility of the color compared with conventional Artificial stone without color change, to obtain improved depth and gloss become.

Of the high density artificial stone of this invention having light storage properties and ultraviolet ray emission characteristics as well as with improved Hue can usually be in any rod-like, cylinder-like etc. shape can be generated.

For this will be selected different molding methods, for example casting molds, molds etc.

When Preßformverfahren is in the lower recording form as a horizontal mold frame so much casting material (mixed material) as necessary previously mixed with as much of the small-particle component, the fine-particle component and the resin component as necessary for the composition after molding, then the upper mold is put on and a surface pressure is applied of 5-100 kgf / cm ² , whereby the compression molding is performed. And in this molding, heating at the time of pressing to a temperature of about 90-140 ° C for about 5-20 minutes.

And in this press molding under heating it is also possible to vibrate the mold frame together with pressure the fluidity of the above mixed material in the mold frame.

This press molding is suitable as a production method on a large scale for comparatively simply shaped disc-shaped Molded articles, and it is very economical as there is almost no loss of material.

And in this invention, it is allowed to roughen the molding surface after molding, So that the finely divided component of the surface part is released.

at the procedure for it will be first used the method for selective removal of the resin component. This means, it is effective, for example, a surface treatment by irradiation the surface of the molded product with water under high pressure after removal from to perform the form.

This treatment is not limitative, as it varies according to various conditions such as thickness, distance from the nozzle, treatment mode, etc. Usually, in the case of a thickness of 2-20 cm, it is possible to produce a hydraulic pressure of 50-1400 kg / cm ² from a nozzle height of about 2-50 cm. This pressure means a lower water pressure condition than in the case of natural stone.

Finally relieved the presence of the resin component makes the production in high quality.

For the nozzle and her System for the ejection of Water under high pressure there are no special restrictions. Various types can be used.

By this surface treatment flattening or roughening is effected by the water jet and an artificial stone with a structure with depth effect generated.

By the presence of the resin component also becomes the disposal of the consumable liquid relieved without the surface becomes white and compared with the etching process, in which chemicals are used.

of course is it is possible if necessary, the surface part with an organic solvent to treat, soften or melt and the resin component partially remove.

In In this case it is possible the organic solvent dependent on from the resin component used, for example from a halogenated hydrocarbon, such as. Methylene chloride, methylene chloride, Chloroform, etc., from a carboxylic acid and its ester compound, such as Acetic anhydride, Ethyl acetate, butyl acetate, etc., or, for example, acetone, tetrahydrofuran, DMF, DMSO etc.

Of the moldings gets into these organic solvents dipped or sprayed with it or with these organic solvents doused, so that the softened or molten resin component from the surface part being removed, it being possible will, surface irregularities train.

Or it is also possible, irregularities in such a way that a part of the resin component, their hardness is low, through a wire brush, scraped off the surface by abrasives, etc.

After roughening and surface treatment by the various means mentioned above, the coating of the small-scale component of the surface is partially broken, thereby causing this coating and particles of the small-scale component to be exposed as a cross-section on the surface portion of the product. This results in a surface structure with unique depth and unique shine. This becomes the unique light reflection phenomenon as mentioned above attributed to men.

The Surface polish agent is not subject to any special restriction, it is possible tools such as grindstone, abrasive cloth, abrasive belt to use or one Abrasive material or Schleifpoliermaterial, a scrubbing agent, etc. to use.

When Abrasive material will suitably be diamond, boron carbide, corundum, Alumina and zirconia, which are mainly a Abrasive action, and tripoly, dolomite, alumina, chromium oxide, Ceria, etc., mainly give a polishing effect.

of course is it after the execution such polishing possible the surface part continue to roughen and irregularities train. In this case, however, this should also be done that, as above mentioned, Particles of at least part of the small particle component and expose the cross section of the coating.

Thereby also becomes an artificial stone with improved light emission properties as well as better surface and structure generated.

1 the attached drawing is a sectional view showing the artificial stone ( 1 ) of this invention. For example, how is 1 shows artificial stone ( 1 ) from a small-scale component ( 2 ) as a transparent inorganic aggregate, a finely divided component ( 3 ) of particles of smaller diameter and a resin component ( 4 ) formed as a binder.

The surface of the small particle component ( 2 ) is coated with light-storing or ultraviolet-emitting substance by burning, and the surface of the artificial stone ( 1 ) polished.

In this construction, the light irradiated from the outside reaches the inner fired coating substance ( 5 ), and when methacrylic resin (MMA resin) having better transparency than resin component ( 4 ) has the consequence that the light on all areas in the direction of the thickness of the artificial stone ( 1 ) meets.

from that follows that incident Light infiltrated into the interior and a light emission from within he follows. All in all, the light absorption layer and the Light emission layer thick. Therefore, the light storage in short Time possible and the light emission efficiency high.

There the coating only on the surface of the small-scale component , it follows that the Use of a small amount of noctilucent or fluorescent Substance is sufficient.

following explain we examples. Naturally This invention is not limited by the following examples.

EXAMPLES

example 1

First, be 50 wt .-%, based on the entire small-particle component, natural Quartz stone with a particle diameter of 10-25 mesh by burning at about 1000 ° C with a surface coating with a thickness of about 30 microns has been provided, wherein Strontiumaluminatbasis light storage material was used with small particle component and calcium carbonate a mean particle diameter of 230 mesh in a weight ratio of 2: 1 and so that they 89 wt .-% of the total weight of the composition, in one mortar with 11 wt% methyl methacrylate (MMA), which is a curing agent in an amount of about 1.5% by weight of the MMA weight, uniformly mixed.

These Composition is poured into a mold frame and made into a plate-like body shaped with a density of about 15 mm.

Subsequently, the surface portion is polished with a diamond-based grindstone and a silicon carbide · magnesia-based grindstone. This has the result that the small-scale component with the fired coating, the partial cross-section of his burned-on layer and the small-scale component uncovered.

Of the resulting artificial stone showed noctilucent in all thicknesses Light storage / light emission characteristics, it has one milky white coloring and marble gloss even at normal depth, no bubbles were in Inside and on the surface present, and the composition was uniform.

At the Test according to the Japanese Industry standard JIS K-7112 resulted in a relative density of 2.29. And the water absorption was 0.13%. Other characteristic features were as in Table 1 below.

Table 1

And Also, there was no anomaly by an acid resistance-alkali resistance test for 8 hours Immersion in 3% aqueous hydrochloric acid solution and for 8 hours Immersed in 3% aqueous sodium hydroxide solution.

By Using the obtained product as building insulation panels it was possible to use walls with a beautiful To obtain granite clay with depth effect.

Example 2

First, be 40 wt .-%, based on the entire small-particle component, transparent Glass with a particle diameter of 5-50 mesh by burning at about 700 ° C with a surface layer with a thickness of about 40 microns has been provided, wherein Strontiumaluminatbasis light storage material was used, small particle component and natural quartz stone powder with a mean particle diameter of 250 mesh are in one weight ratio from 2: 1 and so that they 87 wt .-% of the total weight of the composition, in one mortar with 13% by weight of methyl methacrylate (MMA) (which is a peroxide-based curing agent in an amount of about 2.0% by weight) uniformly mixed. Then this was formed by pressure and heat to a plate-like body with a thickness of 12 mm.

Subsequently, the surface portion is polished with a diamond grindstone and a silicon carbide · magnesia based grindstone, further, only the resin portion of the surface portion is removed at a water jet pressure of 1100 kg / cm ² (nozzle diameter 0.75 mm, jet length 40 mm).

Of the artificial stone normally has depth and roughness, By night, he was through the light storage properties in all Thickness directions visible for a long time.

It was possible Artificial stone effective as noctilucent post construction material for the Emergency to use in case of power failure.

INDUSTRIAL APPLICABILITY

As mentioned above in this invention, a high-density artificial stone is provided, the better Night light features etc and depth and luster and good characteristic Owns properties. About that In addition, the production of such an improved product takes place at a much lower cost compared to traditional ones Products.

Claims (10)

Noctilucent, fluorite or fluorescent artificial stone comprising inorganic aggregate and resin, characterized in that at least part of the inorganic aggregate is a transparent inorganic aggregate, fired or normal temperature coated with a noctilucent, fluorite or fluorescent substance having light storage properties or ultraviolet light emitting properties the surface formulated in an amount of 5-65% by weight of the total amount of the artificial stone. Noctilucent, fluorite or fluorescent Artificial stone according to claim 1, wherein the transparent inorganic Aggregate glass or quartz stone is. Noctilucent, fluorite or fluorescent Artificial stone according to claim 1 or claim 2, wherein 20-80 wt .-% of the formulated inorganic aggregate a transparent inorganic Aggregate is fired or coated at normal temperature with a noctilucent or fluorescent substance on the Surface. Noctilucent, fluorite or fluorescent Artificial stone according to any one of claims 1 to 3, wherein the resin Methacrylic resin is. Noctilucent, fluorite or fluorescent An artificial stone according to any one of claims 1 to 4, wherein the formulated inorganic aggregate of a small-scale component with a Size of 5-70 mesh and a finely divided component having a size of less than 100 mesh wherein at least a portion of the small particle component is a transparent inorganic aggregate, fired or at Normal temperature coated with a noctilucent or fluorescent substance on the surface. Noctilucent, fluorite or fluorescent An artificial stone according to claim 5, wherein 10-100% (weight) of the composition component is a transparent inorganic material, fired or at normal temperature coated with a noctilucent, fluorite or fluorescent substance on the surface. Noctilucent, fluorite or fluorescent Artificial stone according to claim 5, wherein the weight ratio of small-particle component and the finely divided component 1: 1-4: 1. Noctilucent, fluorite or fluorescent Artificial stone according to any one of claims 1 to 7, wherein the thickness the coating of the noctilucent or fluorescent Substance is 5-50 microns. Noctilucent, fluorite or fluorescent Artificial stone according to any one of claims 1 to 8, wherein the proportion of the resin is less than 15% by weight. Noctilucent, fluorite or fluorescent Artificial stone according to claim 9, wherein the proportion of the resin less is 10% by weight.